US4343936A - Process for the preparation of cationic dyestuffs - Google Patents

Process for the preparation of cationic dyestuffs Download PDF

Info

Publication number
US4343936A
US4343936A US06/245,411 US24541181A US4343936A US 4343936 A US4343936 A US 4343936A US 24541181 A US24541181 A US 24541181A US 4343936 A US4343936 A US 4343936A
Authority
US
United States
Prior art keywords
alkyl
water
general formula
azo
represents hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/245,411
Inventor
Harald Gleinig
Bernd Berger-Lohr
Kurt Breig
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Bayer AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Bayer AG filed Critical Bayer AG
Assigned to BAYER AKTIENGESELLSCHAFT, A CORP. OF GERMANY reassignment BAYER AKTIENGESELLSCHAFT, A CORP. OF GERMANY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BERGER-LOHR BERND, BREIG KURT, GLEINIG HARALD
Application granted granted Critical
Publication of US4343936A publication Critical patent/US4343936A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B44/00—Azo dyes containing onium groups
    • C09B44/005—Special process features in the quaternization reaction
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B26/00—Hydrazone dyes; Triazene dyes
    • C09B26/02—Hydrazone dyes
    • C09B26/04—Hydrazone dyes cationic

Definitions

  • the present invention relates to a process for the preparation of cationic dyestuffs of the general formula ##STR3## wherein R 1 represents hydrogen, C 1 -C 4 -alkyl, C 1 - to C 4 -alkoxy, nitro or halogen,
  • R 2 represents hydrogen, C 1 - to C 4 -alkyl, C 1 - to C 4 -alkoxy, halogen or phenylazo,
  • R 3 represents C 1 - to C 3 -alkyl
  • A.sup. ⁇ represents an anion
  • R 3 has the abovementioned meaning, in the absence of organic solvents and in the presence of water, the weight ratio of azo base to water being 100:20-300 and the molar ratio of azo base to dialkyl sulphate being 1:3.5-5.0, and, if desired, by replacing the alkyl-sulphate anion with another anion.
  • the process according to the invention makes it possible to alkylate dye bases of the general formula II rapidly and quantitatively and, in particular, to convert the weak dye bases of the general formula ##STR5## which are formed as intermediates and are difficult to quaternise, quantitatively to the dyestuffs I in a rapid reaction.
  • the process is as a rule carried out in a pH range of 6-10 using acid-binding agents, such as alkali metal oxides, hydroxides, carbonates or bicarbonates or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates, at temperatures between 20° and 100° C. and requires only very short reaction times of about 30 minutes to about 2 to 3 hours.
  • acid-binding agents such as alkali metal oxides, hydroxides, carbonates or bicarbonates or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates
  • An essential criterion for the process according to the invention is the azo base:water:dialkyl sulphate ratio, which in the indicated ranges results in a melt.
  • the preferred weight ratio of azo base:water is 100:50-150 and the preferred molar ratio of azo base:dialkyl sulphate is 1:3.5-4.5.
  • the indicated amounts of water include the water which may be formed during the reaction of the acid-binding agents.
  • dye bases of the formula II it is also possible to use their salts with inorganic or organic acids, for example with hydrochloric acid, sulphuric acid, acetic acid or phosphoric acid.
  • the salts which are obtained when the dye bases are prepared by diazotisation of corresponding aniline derivatives and coupling of the diazo compound with 2,3,3-trimethylindolenine derivatives are preferably used.
  • the dye bases are liberated by adding acid-binding agents in the first reaction step.
  • a particularly suitable embodiment of the process comprises initially introducing the quaternising agent--optionally together with the corresponding amount of water and a portion of an acid-binding agent--and then introducing the azo base, in the dry form or in the form of a moist paste, with the remainder of the acid-binding agent, the quaternising agent for the dye base at the same time serving as the solvent.
  • quaternising agents which may be mentioned are dimethyl sulphate and diethyl sulphate, but especially dimethyl sulphate.
  • halogen is understood as meaning preferably chlorine or bromine.
  • R 1 represents hydrogen, methyl or methoxy
  • R 2 represents hydrogen, methyl, ethyl, methoxy, ethoxy or phenylazo
  • R 3 represents methyl or ethyl
  • A.sup. ⁇ represents methosulphate, ethosulphate, chloride, sulphate, phosphate or acetate or mixtures of these anions.
  • R 1 represents hydrogen
  • R 2 represents hydrogen, methoxy, methyl or phenylazo
  • R 3 represents methyl
  • A.sup. ⁇ represents the abovementioned anions
  • the preferred process can be carried out by, for example, initially introducing the dialkyl sulphate, the corresponding amount of water and a portion of the acid-binding agent and introducing a dye base of the general formula II, in the dry state or optionally in the form of a moist paste, together with the remainder of the acid-binding agent at 20°-50° C., preferably 20°-40° C., at a rate such that the pH value does not fall below 7 and is preferably 7-9.
  • the temperature is then raised to 65°-100° C. in order to effect quantitative conversion, and a virtually homogeneous melt forms.
  • the pH of the reaction mixture is then adjusted to 1-7, and preferably 3-6, with acid, for example hydrochloric acid, sulphuric acid, acetic acid or phosphoric acid, and the mixture is evaporated to dryness, for example in a vacuum paddle drier or spray drier.
  • acid for example hydrochloric acid, sulphuric acid, acetic acid or phosphoric acid
  • the process provides valuable cationic hydrazone dyestuffs which have the fastness properties customary in the trade and have clear, brilliant colour shades. It has the advantage that no effluent is produced.
  • reaction mixture is then heated to 70°-80° C. in the course of about 15-20 minutes, and a homogeneous reaction melt forms.
  • the reaction has ended when no traces or only slight traces of the methylate base formed as the intermediate can be detected by thin layer chromatography. If necessary, further small amounts of sodium carbonate and dimethyl sulphate are added.
  • the pH of the reaction melt is then brought to 4-6 with hydrochloric acid and the mixture is evaporated to dryness in a vacuum paddle drier. About 925 g of dry hydrazone dyestuff of the formula V, with the corresponding content of reaction salts, result.
  • the reaction product can be employed for dyeing without further purification.
  • the dye bases of the general formula II in which R 1 represents hydrogen and R 2 represents hydrogen, p-CH 3 or ##STR8## can also be converted to the corresponding cationic dyestuffs.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Coloring (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cationic dyestuffs of the general formula ##STR1## wherein R1 represents hydrogen, C1 -C4 -alkyl, C1 - to C4 -alkoxy, nitro or halogen,
R2 represents hydrogen, C1 - to C4 -alkyl, C1 - to C4 -alkoxy, halogen or phenylazo,
R3 represents C1 - to C3 -alkyl and
A.sup.⊖ represents an anion,
are prepared by reacting azo bases of the general formula ##STR2## wherein R1 and R2 have the abovementioned meaning, or the salts thereof with inorganic or organic acids, with dialkyl sulphates of the general formula
(R.sub.3 --O--).sub.2 SO.sub.2                             III
wherein R3 has the abovementioned meaning, in the absence of organic solvents and in the presence of water, the weight ratio of azo base to water being 100:20-300 and the molar ratio of azo base to dialkyl sulphate being 1:3.5-5.0, and, if desired, by replacing the alkyl-sulphate anion with another anion.

Description

The present invention relates to a process for the preparation of cationic dyestuffs of the general formula ##STR3## wherein R1 represents hydrogen, C1 -C4 -alkyl, C1 - to C4 -alkoxy, nitro or halogen,
R2 represents hydrogen, C1 - to C4 -alkyl, C1 - to C4 -alkoxy, halogen or phenylazo,
R3 represents C1 - to C3 -alkyl and
A.sup.⊖ represents an anion,
by reacting azo bases of the general formula ##STR4## wherein R1 and R2 have the abovementioned meaning, or the salts thereof with inorganic or organic acids, with dialkyl sulphates of the general formula
(R.sub.3 --O--).sub.2 SO.sub.2                             III
wherein R3 has the abovementioned meaning, in the absence of organic solvents and in the presence of water, the weight ratio of azo base to water being 100:20-300 and the molar ratio of azo base to dialkyl sulphate being 1:3.5-5.0, and, if desired, by replacing the alkyl-sulphate anion with another anion.
The process according to the invention makes it possible to alkylate dye bases of the general formula II rapidly and quantitatively and, in particular, to convert the weak dye bases of the general formula ##STR5## which are formed as intermediates and are difficult to quaternise, quantitatively to the dyestuffs I in a rapid reaction.
The process is as a rule carried out in a pH range of 6-10 using acid-binding agents, such as alkali metal oxides, hydroxides, carbonates or bicarbonates or alkaline earth metal oxides, hydroxides, carbonates or bicarbonates, at temperatures between 20° and 100° C. and requires only very short reaction times of about 30 minutes to about 2 to 3 hours.
An essential criterion for the process according to the invention is the azo base:water:dialkyl sulphate ratio, which in the indicated ranges results in a melt.
The preferred weight ratio of azo base:water is 100:50-150 and the preferred molar ratio of azo base:dialkyl sulphate is 1:3.5-4.5.
The indicated amounts of water include the water which may be formed during the reaction of the acid-binding agents.
In place of the dye bases of the formula II, it is also possible to use their salts with inorganic or organic acids, for example with hydrochloric acid, sulphuric acid, acetic acid or phosphoric acid. The salts which are obtained when the dye bases are prepared by diazotisation of corresponding aniline derivatives and coupling of the diazo compound with 2,3,3-trimethylindolenine derivatives are preferably used. The dye bases are liberated by adding acid-binding agents in the first reaction step.
A particularly suitable embodiment of the process comprises initially introducing the quaternising agent--optionally together with the corresponding amount of water and a portion of an acid-binding agent--and then introducing the azo base, in the dry form or in the form of a moist paste, with the remainder of the acid-binding agent, the quaternising agent for the dye base at the same time serving as the solvent.
Examples of quaternising agents which may be mentioned are dimethyl sulphate and diethyl sulphate, but especially dimethyl sulphate.
In the formulae, halogen is understood as meaning preferably chlorine or bromine.
Preferably:
R1 represents hydrogen, methyl or methoxy,
R2 represents hydrogen, methyl, ethyl, methoxy, ethoxy or phenylazo,
R3 represents methyl or ethyl and
A.sup.⊖ represents methosulphate, ethosulphate, chloride, sulphate, phosphate or acetate or mixtures of these anions.
The process according to the invention is particularly suitable for the preparation of the dyestuffs of the formula I wherein
R1 represents hydrogen,
R2 represents hydrogen, methoxy, methyl or phenylazo,
R3 represents methyl and
A.sup.⊖ represents the abovementioned anions,
and especially for the preparation of the dyestuff of the formula ##STR6##
Compared with known aqueous quaternisation processes which operate with a relatively large weight ratio of water:azo base, for example the process disclosed in DE-OS (German Published Specification) No. 2,262,780, the advantage of the process according to the invention lies in the fact that considerably less quaternising agent is required for quantitative conversion.
Compared with anhydrous quaternisation processes, for example the process disclosed in DE-OS (German Published Specification) No. 2,825,296, considerably shorter reaction times are required in the case of the process according to the invention and, moreover, more complete conversions are achieved.
In detail, the preferred process can be carried out by, for example, initially introducing the dialkyl sulphate, the corresponding amount of water and a portion of the acid-binding agent and introducing a dye base of the general formula II, in the dry state or optionally in the form of a moist paste, together with the remainder of the acid-binding agent at 20°-50° C., preferably 20°-40° C., at a rate such that the pH value does not fall below 7 and is preferably 7-9.
The temperature is then raised to 65°-100° C. in order to effect quantitative conversion, and a virtually homogeneous melt forms.
The pH of the reaction mixture is then adjusted to 1-7, and preferably 3-6, with acid, for example hydrochloric acid, sulphuric acid, acetic acid or phosphoric acid, and the mixture is evaporated to dryness, for example in a vacuum paddle drier or spray drier.
The process provides valuable cationic hydrazone dyestuffs which have the fastness properties customary in the trade and have clear, brilliant colour shades. It has the advantage that no effluent is produced.
EXAMPLE
470 g of the dyestuff of the formula ##STR7## (in the form of the HCl salt) with a solids content of 70% are introduced in portions in the course of 1 hour, at 25°-30° C., into a mixture of 504 g of dimethyl sulphate, 100 g of water and 75 g of sodium carbonate. Simultaneously with the dyestuff, 145 g of sodium carbonate are introduced at a rate such that the pH value does not fall below 7 and is preferably 7-9.
The reaction mixture is then heated to 70°-80° C. in the course of about 15-20 minutes, and a homogeneous reaction melt forms. The reaction has ended when no traces or only slight traces of the methylate base formed as the intermediate can be detected by thin layer chromatography. If necessary, further small amounts of sodium carbonate and dimethyl sulphate are added. The pH of the reaction melt is then brought to 4-6 with hydrochloric acid and the mixture is evaporated to dryness in a vacuum paddle drier. About 925 g of dry hydrazone dyestuff of the formula V, with the corresponding content of reaction salts, result. The reaction product can be employed for dyeing without further purification.
Analogously to this example, the dye bases of the general formula II in which R1 represents hydrogen and R2 represents hydrogen, p-CH3 or ##STR8## can also be converted to the corresponding cationic dyestuffs.

Claims (7)

We claim:
1. Process for the preparation of cationic dyestuffs of the general formula ##STR9## wherein R1 represents hydrogen, C1 - to C4 -alkyl, C1 - to C4 -alkoxy, nitro or halogen,
R2 represents hydrogen, C1 - to C4 -alkyl, C1 - to C4 -alkoxy, halogen or phenylazo,
R3 represents C1 - to C3 -alkyl and
A.sup.⊖ represents an anion,
by reacting azo bases of the general formula ##STR10## or salts thereof with inorganic or organic acids, with dialkyl sulphates of the general formula
(R.sub.3 --O--).sub.2 SO.sub.2
in the absence of organic solvents and in the presence of water and, if desired, by replacing the alkylsulphate anion with another anion, characterised in that the weight ratio of azo base to water is 100:20-300 and the molar ratio of azo base to dialkyl sulphate is 1:3.5-5.0.
2. Process according to claim 1, characterised in that the weight ratio of azo base to water is 100:50-150 and the molar ratio of azo base to dialkyl sulphate is 1:3.5-4.5.
3. Process according to claim 1, characterised in that the dialkyl sulphate, an acid-binding agent and water are initially introduced and the azo base and further acid-binding agent are added.
4. Process according to claim 3, characterised in that the azo base is added in the form of a moist paste.
5. Process according to claim 1, characterised in that the reaction is carried out at pH values of 6-10.
6. Process according to claim 1, characterised in that the reaction is carried out at 20°-100° C. for 30 minutes to about 2 to 3 hours.
7. Process for the preparation of cationic dyestuffs of the formula of claim 1, wherein
R1 represents hydrogen, methyl or methoxy,
R2 represents hydrogen, methyl, ethyl, methoxy, ethoxy or phenylazo,
R3 represents methyl or ethyl and
A.sup.⊖ represents methosulphate, ethosulphate, chloride, sulphate, phosphate, or acetate or mixtures of these anions.
US06/245,411 1980-04-05 1981-03-19 Process for the preparation of cationic dyestuffs Expired - Lifetime US4343936A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3013273 1980-04-05
DE19803013273 DE3013273A1 (en) 1980-04-05 1980-04-05 METHOD FOR PRODUCING CATIONIC DYES

Publications (1)

Publication Number Publication Date
US4343936A true US4343936A (en) 1982-08-10

Family

ID=6099360

Family Applications (1)

Application Number Title Priority Date Filing Date
US06/245,411 Expired - Lifetime US4343936A (en) 1980-04-05 1981-03-19 Process for the preparation of cationic dyestuffs

Country Status (4)

Country Link
US (1) US4343936A (en)
EP (1) EP0037505B1 (en)
JP (1) JPS56155247A (en)
DE (2) DE3013273A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3545605A1 (en) * 1985-12-21 1987-06-25 Bayer Ag METHOD FOR PRODUCING CATIONIC HYDRAZONE DYES

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2164645B1 (en) 1971-12-23 1975-09-12 Ciba Geigy Ag
US3973903A (en) * 1974-03-05 1976-08-10 E. I. Du Pont De Nemours And Co. Azomethine dye solutions
DE2825296A1 (en) 1978-06-09 1979-12-13 Basf Ag Quaternisation of dye bases in absence of solvent - with decomposition of excess alkylating agent with ammonia
US4281112A (en) * 1979-08-04 1981-07-28 Bayer Aktiengesellschaft Process for the preparation of cationic dyestuffs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2164645B1 (en) 1971-12-23 1975-09-12 Ciba Geigy Ag
US3973903A (en) * 1974-03-05 1976-08-10 E. I. Du Pont De Nemours And Co. Azomethine dye solutions
DE2825296A1 (en) 1978-06-09 1979-12-13 Basf Ag Quaternisation of dye bases in absence of solvent - with decomposition of excess alkylating agent with ammonia
US4281112A (en) * 1979-08-04 1981-07-28 Bayer Aktiengesellschaft Process for the preparation of cationic dyestuffs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Chemical Abstracts, Band 83, Nr. 4, 28, Jul. 1975, Pate 98, Nr. 29878s. *

Also Published As

Publication number Publication date
JPS56155247A (en) 1981-12-01
EP0037505A1 (en) 1981-10-14
EP0037505B1 (en) 1983-05-18
DE3013273A1 (en) 1981-10-08
DE3160299D1 (en) 1983-07-07

Similar Documents

Publication Publication Date Title
JPS6140363A (en) Rhodamine dye
NO135587B (en)
US3933847A (en) Method relating to manufacture of coumarin derivatives
US4126610A (en) Process for the preparation of cyano azo dyestuffs
US4806657A (en) Process for the preparation of fluoran compounds which are substituted by basic groups
US4343936A (en) Process for the preparation of cationic dyestuffs
US4760132A (en) Process for preparing cationic hydrazone dyestuffs
DE2302582A1 (en) HYDRO-SOLUBLE AZO DYES OF THE DIAMINO-PYRIMIDINE SERIES
EP0023671B1 (en) Process for the preparation of cationic dyestuffs
US4342867A (en) Process for the preparation of cationic dyestuffs
DE2531445C3 (en) Water-soluble azo dyes free of sulfo groups and their use for dyeing and / or printing synthetic textile fibers
US3991043A (en) Quaternization of benzthiazole-azo compounds
US4269768A (en) Process for the preparation of chlorozincate salts of thiazolium azo dyestuffs
US3936435A (en) Cationic heterocyclic-azo-heterocyclic compounds from 5-aminoimidazo-(1,2-A)pyridines
US4372886A (en) Process for the production of carbinol bases from indoline compounds
US4423226A (en) Zinc chloride complex compounds
US4220780A (en) Cationic dyestuffs
KR840001842B1 (en) Cationic alkylarylhydrazone dyes and methods for preparing the dye bases thereof
US4113717A (en) Quaternized azo dyestuffs
US4165297A (en) Catalyst complex for the preparation of cyano-azo dyestuffs
US4267319A (en) Colored polymeric compounds
US3884899A (en) Water soluble quaternized benzthiazole phenylazopyridine dyestuffs
DE2844606A1 (en) Heterocyclic dyestuffs for natural and synthetic fibre materials - give clear yellow to violet shades with good fastness
EP0036505B1 (en) Process for the preparation of cationic dyestuffs and their use in dyeing acid-modified synthetic fibres
EP0023652B1 (en) Process for the preparation of cationic dyestuffs

Legal Events

Date Code Title Description
AS Assignment

Owner name: BAYER AKTIENGESELLSCHAFT, LEVERKUSEN,GERMANY A COR

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:GLEINIG HARALD;BERGER-LOHR BERND;BREIG KURT;REEL/FRAME:003873/0389

Effective date: 19810305

STCF Information on status: patent grant

Free format text: PATENTED CASE

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M170); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, PL 96-517 (ORIGINAL EVENT CODE: M171); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M185); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 12